Azo-dyestuffs containing chromium and process of making same



Patented July 18, 1933 UNITED --STATES PATENT QFFICE FRITZ STRAUB, OF BASEL, AND HERMANN SCHNEIDER, OF .RIEI-IEN, NEAR BASEL,

SWITZERLAND, ASSIGNORS 'lO .EIRM: SOCIETY OF BASEL, SWITZERLAND OF CHEMICAL INDUSTRY IN BASLE,

AZO-DYES'IUFFS CONTAINING CHROMIULM AND PROCESS OF MAKING SAME No Drawing. Application filed The present invention relates to the manufacture of new azo-dyestuffs containing chromium. It comprises the process of making these dyestuffs as well as the new dyestuffs themselves.

By this invention valuable new dyestuffs containing chromium are obtained by heating in an aqueous solution a mixture of a chromium compound with at least one o-hydroxy-azo-dyestuff, which chromium compound is capable-of forming complex chro mium compounds, and which mixture contains at least two o-hydroxy-azo-dyestuffs, of which at least one is an azo-dyestuff from a l-dia-zo-2-hydroxynaphthalene 4-sulfonic acid and a naphthol, in presence of a proportion of alkali metal ions which neither have a salting out action on the dyestuff, nor unfavorably influence the tinctorial properties of the product, and then evaporating the reaction solution.

The new dyestuffs containing chromium may be regarded as intermediate products of the hitherto known chromium compounds. They are sensitive towards dilute mineral acids in that they partly precipitate forinstance in a dye-bath containing the usual quantities of sulfuric acid, and do not, therefore, yield fast dyeings from such abath. They are further characterized by such an easy solubility in water that they are incapable of being precipitated from the'reaction solution by means of a saturated solution of common salt; They must therefore, if necessary after filtration, be obtained by evaporation of the reaction solution, preferably in a vacuum.

The present chroming process is carried out in such a manner that the mixture of the chromium compound with the o-hydroxyazo-dyestuifs is heated in an aqueous medium. As chromium compounds which are capable of forming complex chromium coinpounds the usual agents yielding-chromium may be used, such as chromium chloride, chromium fluoride, chromium sulfate, chromium sulfite, chromium acetate, chromium formate, chromium hydroxide, a chromium salt of an aromatic sulfonic acid, or the like, or a mixture of any of these chroming agents.

Eoveniber 5,1931, Serial No. 573,300, and in Switzerland November 14, 1930-.

Particularly good results are obtained when chromium oxalate alone or mixed with another chroming agent (for instance a mixture of chromium sulfate or chromium sulfite and chromium oxalate) is used.

Besides these chroming agents, an azodyestuii' containing chromium, made in the usual manner or as described in British Patent No. 364,147 may also be used asa chromof alkali metal ions by means of which the best effect is obtained, must be determined in each case by experiment.

The proportions in which the d used are to be mixed mayvary within wide limits.

The good result of the chroming is, however, dependent not only on the chroming (Bil agent or the proportion of alkali metal ions,

but also on other conditions, temperature, diluent and hydrogen ion concentration, under which the chroming ocsuch as time,

curs; these conditions can be varied in many ways and it is a matter of manlpulative working to determine in favorable conditions.

The new chromium compounds can be used for dyeing animal fibers in the manner simieach case the most lar to that described in the copending specifi- 5: 3

cation Serial No. 482,155, filed September 15, 1930, i. e. conducting the dyeing operation first in weak acid baths, and then developing the dyeings by treatment in dye-baths of strongeracidity. The grey or black dyeings thus produced are fast, particularly to fulling and potting. 'In the second stage, i. e. the development of the dyeings, a new complex is formed on the fiber.

Thenew dyestuffs are useful not only for dyeing animal fibers, but also for printing, for dyeing leather, and for coloring varnishes.

The following examples illustrate the in vention, the parts being by weight Emample 1 303 parts of the azo-dyestufi from nitrated 1-diazo-2-hydroxynaphthalene-4-s u l f o n i c acid and B-naphthol of the formula 98.5 parts of dyestufi from l-diazo-2- hydroxynaphthalene l sulfonic acid and rx-lllPl'lllhOl of the formula are together Suspended in 8000 parts of water. There are added22 parts of caustic soda solution of 30 per cent. strength and 3epart-s of sodium formate followed by a solution of chromium-bisulfite of 4.4 per cent. strength,

corresponding with 76 parts of Cr O and a chromium oxalate solution containing '7 .6 parts of Cr o The whole is now heated and boiled for 28 hours while stirring, whereupon the chromium compound of the three dyestuffs is isolatated by evaporation to dryness under diminished pressure. The product is a dark powder and dyes wool in an acid bath pure black tints of remarkable fastness. Grey tints areobtained if the dyeing is performed in dye-baths of weaker dyestufi concentration.

Example 2 Into'SOOO parts of Water are introduced 308 parts of the azo-dyestufi from nitrated 1- diazo-Q-hydroxynaphthal.ene-4sulfonic acid and B-naphthol, 98.5 parts of the azo-dyestufli tr 0 n1 1-diazo-2-hydroxynaphtha1ene-4-sultonic acid and a-naphthol and 25.2 parts of the azo-dyestufl from 4-nitro-2-diazo-1-phen0l-6-sulfonic and 1-phenyl-3-methyl-5-pyrazolone. After thorough intermixture,there are further added 80 parts of sodium formate, parts of calcined sodium sulfite, followed by a chrome solution corresponding with 83.6 parts of Cr O made by means of 95 parts of crystallized oxalic acid and 63 parts of hy drofiuoric acid of '50 per cent. strength. Nhile stirring well, the whole is brought to the boil and maintained boiling for 2-3 hours. The black violet solution of the chromium complex is then evaporated to dryness on the water-bath under diminished pressure. It dyes wool in an acid bath pure black tints of good'fastness.

If in this example there are used insteadof he 303 parts of the azo-dyestufl from thenitrated 1-diazo-2-hydroxynaphthalene-t-sultonic acid and ,B-naphthol 352.3 parts ofthis dyestuif, and instead of the 98.5 parts of the azo-dyestufi' from l-diazo-Q-hydroxynaphthalenebsulfonic acid and a-naphthol there are used 49.3 parts of this dyestufi, the com plex produced dyes wool black tints which are somewhat more reddish.

Example 3 parts of the azo-dyestufi from 4-nitro-2- diazo-l-phenol-6-sulfonic acid and 1-phenyl= 3-methyl-5-pyrazolone are introduced into 8000 parts of water and there are added 68 parts of crystallized sodium formate, parts of calcined sodium sulfite and then a chrome solution corresponding with 83.6 parts of C130 and made by dissolving'chromium hydroxide paste with aid of 63 parts of crystallized oxalic acid and 115 parts ofsulfuric acid of '93 per cent. strength. After heatine' the solution to boiling, it is maintained in thiscondition for 1 to 2 hours and then the chromium compound is isolated by evaporation ,todryness under diminished pressure. In an acid bath the dyestufi' dyes wool pure black tints'of very good fastness. In this example, the sulfuric acidus'ed for dissolving the chromium hydroxide may be exchanged for the equivalent quantity of hydrochloric acid with a like result.-

- Example 4 I 86 parts of the complex chromiumrcompound obtained as described in Example 1 of British Patent No. 364,147, are dissolved in 900 parts of water, 12.5 parts of the azo-' dyestuff from nitrated 1-diazo-2-h'ydroxy naphthalene 4-sulfonic acid and ,Bmaphthol are added and the whole is boiled for 4 hours in a reflux apparatus. The chrome complex" dyestutlis isolated byevaporating the soludi 'einqca tion undendiminished pressurei' It is'a bla ck powder. very-easily.soluble in water toi a; vio- :QE

- WirOi' black tints of good ftISt-DESSk blaclrisol-ution-s f In ania'cid ibat'h i t dyes I Ewa zii ple 5 A dye bath is prepared with 2000ipartsof (LS parts of formic-acid, which in the Ii hedis'tribu'te'd 'as'desire'd parts of the ch'romimn compound-niade as described in Example 1 of Bri'tislr'Patent NOI36P;147 and part of the dyestufifxfromnitrated 1- diazo2=livdroxvnaphthalene-s esu-lfonic; acid tered at, (3;, dyeing is continuedfor- /ghour andi'n the course ofhalfian h'ourthe hath is tained for'soine' time until the dyestu'ifis exof-concentratedsulfuric acid are added and boiling i'sjcontinued until the color tint is:fullfy.develbped which happens" in about 1 hour. The Word dyed deepblacktints ofqverygoodfastness.

' Ewampljegd- 5 A bath is prepared with 2000 parts of water at a temperature of 85-90 C. and 1 part of formic acid; 100 parts of wool are entered and the liquor is circulated for a short time in a dyeing apparatus; there are then added a further quantity of 12 parts of formic acid and 78 parts of the chromium compounddescribed in Example 1. Dyeing is continued at the same temperature for about 10 minutes and then the bath is raised to the boil and boiled for minutes. There are then added two parts of concentrated sulfuric acid diluted with water in the course of 10 minutes, and after a further 20 minutes 6 parts of concentrated sulfuric acid diluted with water are added. The dyeing is developed by boiling for 1 hour. The wool is dyed black tints of very good properties of fastness.

hat we claim is 1. A manufacture of chromiferous dyestuffs. wherein a mixture of a chromium com pound with orthohydroxyazodyestuifs, which chromium compound is capable of forming complex chromium compounds, and which mixture contains at least two ortho-hydroxyazodyestuffs, of which at least one is an azodyestuff from a 1-diazo-Q-hydroxynaphthalenet-sulfonic acid. and a naphthol, is heated in an aqueous solution and in presence of such a proportion of alkali metal ions as will neither serve to salt out the dyestufi', nor exert an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solution to dryness.

2. A manufacture of chromiferous dyestuffs. wherein a mixture of a chromium compound with orthohydroxyazodyestufi's, which chromium compound is capable of forming complex chromium compounds, and which ustufifs, whereina mixture of mixture contains an azo' d yestuff I from the ni- -trated 1 diazosQ hydroxyrraphthalene-t sulfoni'cacid and a naphtholand an azo-dyestuff from i the 1 diazo 2hydroxynaphthalene lsulfronic acid andia" naphthol, isheat'ed in an zzaqueousflsoliutiongi and in presence of sucha proportion of all ral-i metal ions as will neither serve to salt out'thedyestuff; nor exert an: un- -fav'orableinfinence on the tii'rctorial: properties of the product, and then evaporating the 'reaction solution to dryness. 1

w 3.,A manufacture of chromiferous *d'yea chromium compound with orthohydroxyazodyestuffs,which =Jchromi=umcompound is capable of forming complex chromium .rcompoundd and wh ch mixture contains the az'o -dyestufi' from theznitrated *1 -diaz'o'#2 hydroxynaphthaleneA suled-in an aqueous solution, and iir-pres-encebf such a' proportion of-a l lra'li me'tal'ions as will neither serve to salt-out the dyestufi', nor exert i an unfavorable influence on the I tinctorial properties-of the-product; andthenevaporating the reaction solution to dryness.

4. A manufacture of a chromiferous dyestufl', wherein a mixture of the dyestuff containing chromium from the nitrated l-diazo- Q-hydroxynaphthalene--sulfonic acid and ,B-haphthol, with the dyestuff from the nitrated 1-diazo-2-hydroxynaphthaleneA-sulfonic acid and ,B-naphthol, is heated in an aqueous solution, and in presence of such proportion of alkali metal ions as will neither serve to salt out! the dyestufi', nor exert an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solutionto dryness.

5. The new chromium compounds which are obtained by heating a mixture of a chromium compound with ortho-hydroxyaz'odyestuffs, which chromium compound is capable offorming complex chromium compoundsf and which mixture contains at least two orthohydroxyazodyestufl's, of which at least one is .an azo-dyestuff from a 1-diazo-2-hydroxynaphthalene--siilfonic acid and a naphthol, in an aqueous solution, and in the presence of such a proportion of aklali metal ions as will neither serve to salt out the dyestufl, nor exert an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solution to dryness, which products are dark to black powders which are very easily soluble in water, and dye wool grey to black shades of very good fastness.

and which Inixturecontains an azo-dyestulf till) 6. The new chromium compounds which from the nitrated 1-diazo-2 hydroxynaphthalene-l-sulfonio acid and'anaphthol and an azo-dyestuff from the -1-diazo2-hydrox'ynaphthalene-L-sulfonic acid and a naphthol, in an aqueous solution, and in the presence of such a proportion of alkali metal ions as will neither serve to salt out the dye'stufi, nor exert an unfavorable influence on thetinctorial properties of the product, and then evaporating the reaction solution to dryness, which products are dark to black powders which are very easily soluble in water, and

dye wool grey to black shadesof very good i will neither serve to salt out the dyestufi, nor

exert, an unfavorable influence on the tinctorial properties of the product, and then evaporating the reaction solution to dryness, which products are dark to black powders which are very easily soluble in water, and dye wool grey to black shades of very good fastness; 4

8. The'newchromium compound which is obtained by heating a mixture of the dyestufi containing chromium from the nitrated l-diazo- 2 -hydroxynaphthalene -sulfonic acid and ,B-naphthol with the dyestufffrom the nitrated 1-diazo-2-hydroxynaphthalene- -s'ulfonic acidand fl-naphthol, in an aqueous .solution, and in the presence of such a proportion of alkali metal ions as will neither serve to salt out the dyestufl', 'nor exert an unfavorable influence on the tinctorial properties'of the product, and then evaporating the reaction. solution to dryness, which product isa black powder which is very easily soluble in Water, and dyes wool grey to. black shades of very good fastness.

' HERMANN SCHNEIDER.

FRITZ STRAUB. 

